DE2736205A1 - WATER VAPOR ABSORBENT AND WATER VAPOR PERMEABLE AREA MADE OF RUBBER AND A PROCESS FOR ITS MANUFACTURING - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT

KALLE branch of Hoechst AG K 2568 + H Wiesbaden-Biebrich

Water vapor absorbent and water vapor permeable Flat structure made of rubber and a process for its production

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

- / ■

The invention relates to a planar structure with improved water vapor absorption capacity and permeability of natural or synthetic rubber or a rubber-like polymer and method of manufacture this flat structure.

Flat structures made of rubber are used on various technical fields applied, including z. B. the production of rubber shoes, sponge and cellular rubber,

IO rubberized fabrics (e.g. raincoats, tents, or

Carpet backing) or dipped rubber goods (e.g. surgical gloves). Method of manufacture such flat structures, which are usually as self-supporting films or as multi-layered (e.g. from cover and Flat structures (consisting of a carrier layer) have been known for a long time (see, for example, Ullmann's Encyclopedia der technical chemistry, Verlag Urban & Schwarzenberg - Munich, 1957, Volume 9, 3rd edition, keyword "Rubber", in particular pages 351 ff, 365 ff and 375 ff

20 or S. Boström, Kautschuk-Handbuch, Verlag Berliner

Union - Stuttgart, 1961, Volume 4, 1st edition, in particular pages 172 ff and pages 263 ff). Are these fabrics used in particular under physiological conditions, d. H. for example as a coated textile or as a shoe and in the form of a sponge (foam) rubber for shoe insoles, or cushioning materials One of the key requirements for the material is that it is capable of absorbing water vapor and, if possible, also is still permeable to water vapor, for example on the

30 body to produce good wearing comfort.

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H - / -

Since the fabrics mentioned are often used in areas where a water-repellent Effect should be achieved and you can do so successfully at a relatively low price 5 often the associated disadvantage of non-absorption or non-permeability of water vapor (e.g. from Sweat) accepted. But there has been no lack of attempts to remedy this obvious deficiency, In particular, attempts were made to reduce the porosity of the sheet-like structures to increase. By this measure, i. H. usually the introduction of additional pores in the Flat structures made of rubber, however, the structural strength of the materials produced from them is reduced and in some cases the water-tightness of the materials, which is required per se, cannot be maintained either will. It is used in these foamed sheet-like structures Although a certain water vapor permeability has been observed, there is no significant water vapor absorption ascertain.

From DT-PS 910 960 a method for producing porous highly absorbent sheet-like structures is known, the products supplies the artificially created fine and finest pores in addition to the cavities that usually form

25 and which should therefore be absorbent. the

The additional fine pores are generated with water-soluble substances that enter the fabric during the process Manufactured in finely divided form and incorporated from the fabricated structures, leaving behind fine pores be released again. Water-soluble organic substances such as starch and protein serve as pore formers

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H -Z-

or protein-like substances, sugar, tragacanth, cellulose derivatives and synthetic resins, or those substances which become water-soluble through the action of ferments or enzymes. In the production of the sheet-like structure, the base material made of fleece is impregnated with an impregnating agent Contains pore-forming agents, treated; as an impregnating agent can be aqueous dispersions or emulsions of vulcanizable substances, such as natural rubber, synthetic rubber or synthetic resin can be used.

In the DT-AS 12 04 186 a method for the production

a window leather-like, absorbent, porous, coated fabric described in which a mixed fabric from Cotton and ZeIlwol1 fibers into the inner area the fabric threads roughened, then the mixed fabric cleaned and desized, then the roughened Fibers of the mixed fabric with a paste of natural or synthetic rubber latex, one the viscosity increasing substance and an easily soluble salt suitable for pore formation, thinly coated on one or both sides and finally the fabric is dried and the pore former is washed out. As the viscosity Enhancing substances are listed as pore builders, karagum, tragacanth, starch, dextrans and gum arabic

25 Sodium Sulphate and Chloride.

The hydrophilic structure made of a fiber and film-forming, water-insoluble polymers according to DT-OS 64 628 has particles of modified cellulose ether on. The following are named as polymers: regenerated

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H - / ζ -

Cellulose (cellulose hydrate), cellulose acetate, polyalkylene, Alkyl cellulose, polyacrylonitrile, polyamide and polyester. The modified cellulose ethers are those, their mere Degree of etherification lead to water-soluble cellulose ethers and which have been modified in such a way that they have become at least for the most part water-insoluble, but for the Have remained capable of absorbing water. The hydrophilized The structure has the particles of modified cellulose ether evenly distributed in its polymeric mass or a surface covered with the particles. as technical fields of application for such-hergestel1 te Films are listed as being used as ion exchangers or as dialysis or osmosis membranes.

The invention is based on the object of providing a water vapor absorbent that is improved over the prior art and to propose a permeable sheet-like structure based on rubber.

The invention is based on a water vapor absorbent and permeable sheet-like structures made of natural or synthetic rubber or a rubber-like one Polymers with an evenly incorporated addition of polymer particles. The planar structure according to the invention is characterized in that it contains particles of at least one swellable, modified polymer as an additive contains. The term "evenly incorporated" is to be understood as a statistical distribution. That Polymers is in particular at least about 50 wt .-%

30 insoluble in water.

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H

In a preferred embodiment, the sheet-like structure contains about 5 to 30% by weight, based on the rubber content, on the addition of the particles of at least one swellable, modified polymer. The particles have expediently a size of ^ 250 pm, in particular = 150 pm and are generally in powder or fibrous form,

As swellable, modified polymers for addition in the materials according to the invention, for example suitable for:

Crosslinked polyalkylene oxide according to DT-OS 20 48 721; at the Process for making this product are water-soluble polyalkylene oxides with a sufficiently strong ionizing radiation to achieve crosslinking and insolubility of the polymer. the Irradiation can be done with the polyalkylene oxide in solid State or in solution.

²⁰ The absorbent, cross-linked, carboxyl-containing

Copolymer according to DT-OS 25 07 011 from a <? G, ßunsaturated Acid and an acetal of the general formula

(CH ₂ = CH-CH ₂ -O) ₂ - CH - (CH ₂ J _n - CH - ( _{O-CH 2} -CH = CH ₂ ) ₂

where η = 0, 1 or 2. Acrylic acid, methacrylic acid, itaconic acid, ÖC-phenylacrylic acid or ^ .- benzylacrylic acid are particularly suitable as <7C, β-unsaturated acids; In the preparation of the copolymer, it is advantageous to use 0.1% to 15 % of the acetal for 85% to 99.9% of one of the unsaturated acids.

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

A hydrocarbon polymer disclosed in U.S. Patent 3,670,731 (= DT-OS 16 42 072), which is water-insoluble due to crosslinking was made and is suitable to absorb and also to hold back liquids; are mentioned in particular certain polyacrylamides, alkali metal salts of hydrolyze polyacrylamides and alkali metal salts of Polystyrene sulfonetes.

A water-swellable, crosslinked, insoluble, physiologically harmless polymer according to US Pat. No. 3,669,103 (= DT-OS 16 17 998) from the group of poly-N-vinylpyrrolidones, Polyacrylamides, polyacrylic acid and polyglycols.

Manufactured according to the method of DT-OS 25 41 035, at least for the most part water-insoluble, with water swellable absorbent polymers which are produced in such a way that in a homogeneous phase polyhydroxymethylene in aqueous-alkaline solution with an oC-halocarboxylic acid etherified and before, during or after the etherification with an opposite polyhydroxymethylene in an alkaline medium converts polyfunctional crosslinking agent.

In particular, the following are swellable, modified ones Carbohydrate derivatives can be used in the context of the invention: Al kaiimeta11 salts of carboxymethyl cellulose, which are heat-treated and are swellable in water according to US Pat. No. 2,639,239; in the process of making this Product is the solubility of a water-soluble alkali metal salt of carboxymethyl cellulose, which is a

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H - # -

D.S. (= Degree of substitution, i.e. number of substituted Hydroxyl groups on an anhydro-o-glucose unit) of 0.5 to about 1, reduced by this dry salt in finely divided form at a temperature of exposing about 130 ° to about 210 ° C, with high swellability Gel particles are obtained.

Water-insoluble, absorbent and retentive liquids heat-treated carboxyalkyl celluloses according to the U.S. Patent 3,723,413 (= DT-OS 2,314,689); the procedure for making these products is such that one

a) Cellulose materials with carboxyalkylating Respondents treated and thereby

water soluble carboxyalkyl cellulose with a mean degree of substitution of more than 0.35 carboxyalkyl radicals per anhydroglucose unit in the Cellulose, but with poor liquid absorption and retention properties

20 forms,

b) such a part of the carboxyalkylating Reactants and by-products formed during the reaction removed that, based on the weight of the water-soluble carboxyalkyl cellulose, at least about 3% by weight thereof remain, and

c) the carboxyalkyl cellulose in the presence of the remaining carboxyalkylating reactants and by-products of the reaction of heat treatment

909808/0273

A4

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

subjects and thereby renders them water-insoluble and their excellent properties in relation to Imbues absorption and retention of liquids.

Absorbent carboxymethyl cellulose fibers for use suitable in fiber materials for the absorption and retention of aqueous solutions and essentially insoluble in water are according to US Pat. No. 3,589,364 (= DT-OS 1 912 740); such fibers consist of wet-crosslinked fibers of water-soluble salts of carboxymethyl cellulose with a D.S. from about 0.4 to 1.6 and have the original fiber structure. Used as a crosslinking agent preferably about 3-10% by weight of epichlorohydrin are used.

Chemically cross-linked, swellable cellulose ethers according to U.S. Patent 3,936,441 (= DT-OS 2,357,079); these crosslinked cellulose ethers, in particular from carboxymethyl cellulose, Carboxymethyl-hydroxyethyl cellulose, hydroxyethyl cellulose or methyl hydroxyethyl cellulose are produced in such a way that the ethers, which are water-soluble in themselves, are in alkaline Reaction medium to be reacted with a crosslinking agent, its functional groups

25 the acrylamido group CH ₂ = CH-CN ^

tO ('the chloro-azomethine group -N = C- or

lCl I

30 the allyloxy-azomethine group -N = C- (J-CH ₀ -CH = CH ₀

ι - cc

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

are or the dichloroacetic acid or phosphorus oxychloride is.

Chemically modified, swellable cellulose ethers according to the U.S. Patent 3,965,091 (= DT-OS 2,358,150); these cellulose ethers, which have not been modified by crosslinking, become like this produced that the per se water-soluble ether in an alkaline reaction medium with a monofunctional reacting compound, which is described by one of the following two general formulas:

I CH ₂ = CH - CO - NH - CH - R ₁ or

R ₂

II CH ₂ = CH - SO ₂ - NH ₂ ,

where in formula I: R. = the hydroxyl, an acylamino or an esterified carbamino group and R ₂ = hydrogen or the carboxyl group.

Chemically cross-linked, swellable cellulose ethers according to DT-OS 2,519,927; These cross-linked cellulose ethers are produced in such a way that the water-soluble ethers are in alkaline reaction medium can be reacted with bisacrylamidoacetic acid as a crosslinker.

Free flowing hydrophilic carbohydrates that are crosslinked by radiation and swell in water according to DT-AS 2 264 027; these products are manufactured in such a way that (with

909808/0273

HOECHST AK TIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H

the following reaction stages can also be carried out with certain other polymers, such as polyethylene oxide or polyvinyl alcohol, similar products are obtained):

5 a) at least one water-soluble powdery

polymeric carbohydrate with such an amount of at least one powdery inert filler, whose particles are smaller than those of the carbohydrate, mixed so that a substantial part of the The surface of the powdery carbohydrate is covered,

b) while continuing to mix the mixture with thorough stirring with a finely divided water spray in an amount such that the mixture is in a free flowing particulate form is preserved, and

c) then the mixture obtained up to the crosslinking of the polymeric carbohydrate by ionizing radiation

20 suspends.

Chemically crosslinked or otherwise modified, swellable Starch ether according to the DT note. P 26 34 539.1; these special starch ethers are manufactured so that, for. B. as a modification, crosslinking with a crosslinking agent is carried out, which carries the following functional group which is reactive towards hydroxyl groups:

H 30 \

C = C the acrylamido group, where

IOi

R ₁ = H or CH,

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

or

an o6 ~ halo-epoxy group, where Hai = Cl or Br

or

-N = C

the chloro-azomethine group

Cl

or

-N =

C-O

1 -

- CH ₉ - CH = CH

the allyloxy-azomethine group

or is the phosphorus oxychloride. Another kind of Production proceeds in such a way that the modification with one under the conditions mentioned compared to the Hydroxyl groups of the starch or of the starch ether is carried out monofunctionally reactive compound, which is described by one of the following general formulas:

C-N-R.

I ο,

or

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

where R ₁ = CH ₃ or H and R ₂ = H and R ₃ = CH ₃ , CH ₂ -OH, an N-methylene-acylamido group with 1 to 3 carbon atoms, an esterified N-methylene-carbamido or N- Is carboxymethylene carbamido group with 2 to 7 carbon atoms, or R ₂ ^{un <} * ^R 3 ⁼ CH ₃ or CH ₂ -OH and where R ₄ and R ₅ = H or R ₄ = H and R ₅ = CH ₃ or R ₄ and R ₅ = CH ₃ .

Al kaiimetal1 salts of carboxymethylcellulose with increased

Absorbance and retention capacity according to US Pat. No. 3,678,031 (= DT-OS 21 51 973). It is true that etherifying agents containing carboxyl groups are used, which have a normal

2Q would result in soluble cellulose ethers, but the conditions of the reaction were chosen so that alkali metal salts of carboxymethyl cellulose with a DS of 0.4-1.2, a water-soluble fraction of <35 %, a water retention value (WRV) of about 1,000 to 7,000 and a salt water retention value of around 400 to around 2,500 arise.

Water-insoluble carboxymethyl celluloses such as those in the DTPS 10 79 796 and DT-AS 11 51 474 can be used, i.e. H. those of a D.S. from 0.05 to 0.3 and those of the im

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

are essentially insoluble in water and also have a have low D.S.

Water-insoluble, more highly polymerized carboxymethyl or carboxyethyl cellulose with a substantial content of free carboxyl groups according to GB-PS 725 887 (= DT-PS 10 37 076) which are made water-insoluble by heating the water-soluble, acidic compounds to 80 ° C to 177 ° C .
IO

Phosphorylated cellulose fibers according to DT-OS 24 47 282, as they do by reacting cellulose pulp with urea and phosphoric acid under the action of heat, a subsequent acid hydrolysis and a final top pass can be produced in the salt form.

Dry, solid, water-swellable, water-insoluble Absorbent according to DT-OS 26 09 144, which consists of an ionic complex of a water-insoluble anionic Consist of polyelectrolytes and a cation of an at least trivalent metal; as polyelectrolytes are polyacrylic acid, Starch or cellulose derivatives are suitable.

Celiulose graft polymers according to DT-OS 25 16 380, the be prepared in that the cellulose side chains are grafted from such polymer residues, which are made of the ionic and nonionic polymer residues are selected. Suitable for this are, for example: polyacrylic acid, Sodium polyacrylate, polymethacrylic acid, potassium polymethacrylate, Polyvinyl alcohol sulfate, polyphosphoric acid,

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H

Polyvinylamines Poly (4-vinylpyridine), hydrolyzed Polyacrylonitrile, polymethyl methacrylate, polyvinyl acetate, polystyrene or polybutadiene.

Granulated, water-insoluble alkali metal carboxylate salts of starch-acrylonitrile graft copolymers according to US Pat. No. 3,661,815, which are obtained by saponification of starch-acrylonitrile graft copolymers be prepared with a base in an aqueous alkaline medium.

Modified cellulose material with improved retention capacity for both water and physiological fluids according to DT-OS 25 28 555, that by grafting an olefinically unsaturated, polymerizable monomer with hydrolyzable functional groups or a functional Carboxyl group-bearing monomers on a fibrous cellulosic material and hydrolyzing or otherwise Treating the grafted product with alkali. The product is initially in the State of maximum swelling, then acidified to a pH value at which it is the state of minimum swelling possesses, then converted into the salt form under conditions which do not cause swelling and finally dried.

Modified polysaccharide according to DT-OS 26 47 420, produced from polysaccharide, acrylamide, another vinyl monomer and a divinyl monomer among radicals Reaction conditions.

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H

The process for the production of fabrics from Rubber are known. The flat structure can be a be self-supporting film or by coating or Impregnation of a base made of natural or synthetic fiber material, non-woven fabrics or synthetic resin sheets are produced; the rubber content can be in both solid and foamed form. Can be used for coating or impregnation preferably use the following documents:

Woven or non-woven textile materials from one or more components, e.g. B. made of synthetic fibers such as polyamides, polyesters, polyacrylonitrile, PVC, polyolefins, Polyamino acids, as well as from glass fibers, regenerated fibers such as viscose fibers, acetate fibers and the like., Made from natural fibers such as cotton, silk, wool, linen and collagen, obtained by rubbing natural leather; or sheet-like materials composed of one or more components, e.g. B. from synthetic Resins such as polyamides, polyesters, polyacrylonitrile, PVC, Polyolefins, polyamino acids, or from natural leather from which the silvery surface has been removed, or from Waste leather contains collagen, natural rubber and synthetic rubber.

The bases can be coated or impregnated by various processes, and there are also various processes Process for the production of self-supporting foils possible. The basic material for the production of the planar structure according to the invention is rubber. The generic term rubber includes, for example, the following sub-terms

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H

To be understood: latex made from wild or plantation rubber, pre-vulcanized latex, Positex (latex, its negative Charge has been converted into a positive), rubber and regenerated dispersions, raw rubber types such as "Smoked" Sheets "and" Crepe ", synthetic rubber types such as copolymers of butadiene with styrene and des Butadiene with acrylonitrile, polymers and copolymers of chlorobutadiene, polymers and converted Polymers of vinyl compounds, copolymers of isobutylene with isoprene, block polymers of butadiene, Thioplasts, silicone rubber, regenerated rubber, Factice and others.

The processing of the rubber can generally be carried out as follows:

The processing of latex is done in such a way that first the vulcanizing agents and other auxiliary products such as Fillers, anti-aging agents, plasticizers, etc. in the Latex can be stirred in, then, for example, after the immersion process with or without coagulants, the foaming process, by electrophoretic deposition, the impregnation process or the brushing process the desired fabric can be produced.

Solid rubber is processed in such a way that the raw rubber bales are first crushed, the Rubber is plasticized and the mixture to be processed is produced with customary auxiliary products, finally can then for example by calendering, frictioning

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

and dipping or spreading rubber solutions, the desired sheet-like structure can be produced, finally the rubber film or the rubber-containing layer is vulcanized.
5

When carrying out the examples, the procedure described below was followed in particular (parts are parts by weight, percentages are given in% by weight):
IO

1 A rubber textile coating is created by dissolving 30 parts of the following on one Roll produced, vulcanizable mixture in 70 parts of a gasoline / toluene mixture 60 parts of gasoline and 10 parts of toluene.

60.0 % Smoked Sheets 10.0 Il Fact is 20.0 Il soot 6.0 Il zinc oxide 1.5 Il sulfur 1.0 Il Vaccination accelerator 1.0- « Anti-aging agents qJI m ^ Ibaric acid

Voi ^^^^^ Bpireichen or something else The solution will process the particles of at least one modified, swellable Added to polymers and evenly distributed therein,

then the mixture is spread or

deformed differently and finally for about 30

vulcanized at about 120 ° C. 9098Ö8 / 0273

ORIGINAL INSPECTED

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

A foam rubber is created from

100.0 parts crepe

10.0 "zinc oxide

60.0 "chalk filler

15.0 "mineral oil

2.0 "paraffin

3.0 "stearic acid

1.0 "mold release agent

3.5 sulfur

1.5 "vulcanization accelerator

1.0 "anti-aging agent

5.5 "propellant paste

15 Before foaming and vulcanizing this Mixture of the particles of at least one modified, swellable polymer added and therein equally distributed.

20 3 latex foam parts can be made from natural latex or synthetic leather as follows, wherein the particles of at least one swellable, modified polymer before the Au fs ^ aMRn, the Coagulation and vulcanization

about 4 times the water depth a Latex mixture is added and in it.

ORIGINAL INSPEGTEO 909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

3.1 The natural latex mixture consists of:

167.0 parts of 60% natural latex

3.5 "20% aqueous sodium stearate solution

5 3.0 "10% aqueous dispersant solution

2.5 "sulfur

1.6 "vulcanization accelerator

7.8 "5% aqueous emulsifier solution

2.5 "zinc oxide

0.8 "anti-aging agent

4.0 "thickener

3.0 "15% aqueous foam stabilizer solution

For coagulation, 15

20.0 parts of 10% strength aqueous ammonium chloride solution

given.
3.2 The synthetic latex mixture consists of:

74.0 parts Buna latex

2.2 "K-oleate

9.0 "vulcanizing paste

5.0 "methyl cellulose

For coagulation, the mixture mentioned

Added 2.0-4.0 parts of silicon fluoride. 30th

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H -JiAT-

In order to produce the planar structures according to the invention, the particles to be processed are made of at least one modified, swellable polymer, preferably in a proportion of 5 to 30% by weight, based on the finished film or the Layer or the rubber content in the layer, added and evenly distributed therein; the mixture is then spread or otherwise deformed.
10

The planar structures according to the invention have good properties Ability to absorb and permeate water vapor which goes far beyond a pure transport effect of the incorporated particles. In addition, are the fabric is also able to absorb the water vapor under certain conditions, For example, staying in a different climate, to give it up again.

Because the mentioned properties of the fabric are not solely on the significantly demonstrable effect through the addition of the particles from at least one swellable, modified polymers are based, but inter alia. also depend on the thickness of the film or coating these are expediently produced in a thickness of about 0.05 to about 0.5 mm, especially when next to a good water vapor absorption capacity should also achieve good water vapor permeability.

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H -Ji * -

The planar structures according to the invention with the aforementioned Properties are, for example, as a self-supporting film or as a coating on a base, in particular as a rubberized textile, shoe upper material, shoe insole, 5 or carpet backing materials, i.e. for such areas of application suitable where, under physiological conditions, body fluids such. B. sweat, appear. In foamed form they can also be used as absorbent for hygiene articles, such as. B. tampons are used as they can also absorb and hold back water as foam.

Among those in the description and the examples for characterizing the planar structures according to the invention and The parameters used in the swellable polymers present in them are to be understood as follows:

WRV water retention capacity of the swellable, modified Polymers in wt .-%, measured against 2000 times the acceleration of gravity, based on its water-insoluble Proportion of; the WRV is determined after immersing the sample in water,

WUA water-insoluble part in the swellable modifi-25 adorned polymers,

DS degree of substitution, number of substituted hydroxyl groups on the anhydro-D-glucose units, from 0.0 to 3.0

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

SV pumping speed of the swellable modified polymer for 1% NaCl solution in% by weight, based on Total weight; the SV is determined after 1% aqueous NaCl solution has been absorbed by the sample to saturation.

_{01n The water vapor absorption is determined by the weight loss of a sample dried to constant} weight under the conditions according to DIN 53 304 (May 1968 edition) at 102 ° C + 2 ° C,

based on the original weight. The sample is initially in the delivery condition immediately after removal from a water-vapor-tight container to an accuracy of 0.001 g weighed. The specimens are then heated

Dried in a cupboard at 102 ° C + 2 ° C for 15 h and after cooling to room temperature also weighed to the nearest 0.001 g. To determine the water vapor absorption capacity of samples to be able to test different conditions,

the respective samples are hung in different climates and after certain times these are removed and then their water vapor absorption in% by weight, based on their initial weight at the beginning of each measurement, he

averages.

Water vapor permeability (according to W. Fischer and W. Schmidt, "Das Leder", E. Roether-Verlag Darmstadt, 2Λ 87 ff (1976)). Within the

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H -JVS -

Apparatus has a temperature of 32 ° C, above the sample a standard climate - unless otherwise stated - of 23 ° C / 50 % relative humidity, that of a fan attached above the device through a light air

current is always kept constant. The free test area is 10 cm ² . Inside the apparatus, too, the water at 32 ° C. and the atmosphere above it, which is saturated with water vapor, is constantly heated with the aid of a magnetic stirrer

Movement kept. The WDD is determined by determining the weight loss of the test vessel with the sample. The WDD is given in mg / cm ² • χ h (x mostly 1, but also 8 or 24).

WDAppj water vapor absorption (see also WDD _p pr). The water vapor absorption is carried out at the same time as the WDDppj measurement, the determination is made by determining the weight increase of the sample; unless otherwise stated,

is the sample permeable to the outside climate, d. H. it is not covered.

In all of the following examples, modified, swellable polymers with bisacrylamidoacetic acid chemically crosslinked sodium carboxymethyl celluloses with the following parameters WUA = 70%, WRV = 400 to%, SV = 800 to 1,400 %, DS = 0.8 to 1 were used as representative , 1 and a particle size of = 200
of = 100 pm is used.

Particle size of = 200 μπι, with a proportion of 90 wt .-%

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

K 2568 + H - 2fr -

Examples 1 to 3 and comparative example V1 (Table I)

According to the invention, it is a rubber-coated textile fabric made of cotton with an additive in the layer of modified, swellable polymer in various Amount of 15% by weight (example 1), 20% by weight (example 2) and 25% by weight (Example 3), based on the weight of the rubber layer, prepared and with such without an additive (V1) compared with regard to water vapor permeability and water vapor absorption. With an increasing proportion of modified, These values increase with swellable polymer; in the cases carried out, there are no significant values Influence on the mechanical properties of the coated fabric. The coated according to the invention In comparison with the coated fabrics without an additive, fabrics with an additive have a clear water vapor permeability and water vapor absorption.

Examples 4 to 6 and Comparative Examples V2 to V4 (Table II) 20

According to the invention, there is a foam rubber made from a rubber compound (in various thicknesses) with an addition of modified, swellable polymer in a proportion of 15% by weight, based on the weight of the foam rubber, produced and with a foam rubber of the same thickness without additive with regard to the increase in water vapor absorption increasing exposure time of the water vapor compared. The foam rubbers have the following structure:

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

Example V2 and Example 4: wear both outer surfaces

a rubber skin

Example C3 and Example 5: an outer surface shows an open foam, an outer surface

surface has a rubber skin

Example V4 and Example 6: both outer surfaces show one

open foam IO

A foam rubber made according to the invention with an additive absorbs more water vapor than a similar type of foam rubber without additives.

15 Example 7 and Comparative Example C5 (Table III)

According to the invention, a foam made from natural latex is used an addition of 15% by weight of modified, swellable Polymers, based on the weight of the finished latex foam, produced (Example 7) and with such without addition (V5) regarding the water vapor absorption in different climates and with increasing exposure time of water vapor compared. A manufactured according to the invention Foam made of latex with additive decreases significantly

25 more water vapor than a similar foam without additives.

Examples 8 to 10 and Comparative Example C 6 (Table IV) According to the invention, a foam made from synthetic latex is used

909808/0273

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

an additive in various amounts of 10% by weight (Example 8), 20% by weight (Example 9) and 30% by weight (Example 10), based on the weight of the finished latex foam, and with one without Addition (V6) compared with respect to water vapor absorption. The foams are exposed to a humidity of 65 % relative humidity (RH) at 20 ° C. and then to various humidity levels, and the respective increase or decrease in humidity is measured after a certain period of time. As the amount of additive increases, so does the water vapor absorption capacity of the foam; a foam with an additive absorbs significantly more water vapor than a similar foam without an additive.

909808/0273

to

ro

Table I.

co O (O OO O OO

u>

example Strength of the sample WD Dppj in WDA _pFI in Weight * V1 (mm) mg / cm ² x 8h mg / cm ² * h mg / cm ² - 8h 0.44 1 Rubber layer 0.2
Fabric layer 0.4 0.55 0.07 0.60 2.61 CVJ Il 2.79 0.35 3.03 10.85 3 Il 2.83 0.35 11.87 23.57 Il 20.50 2.56 19.59

ro
cn

co

ro η

M 32

OZ (D
O Ω

cn M rt
cn

η η tr ¹ tr ¹

■ cn O

CD N) O

cn

NJ

Table II

example Strength of the sample Size of the sample Increase in 2h WDA ₀₁ Y in% by weight 12h ' after V2 (mm) (mm ² ) 1h 0.05 4h 8h 0.16 24 hours ' 4th 25th 50 · 100 0.03 0.17 0.07 0.12 0.61 0.25 V3 25th Il 0.11 0.14 0.27 0.45 0.50 0.95 5 5 Il 0.10 0.68 0.23 0.37 U90 0.82 V4 5 Il 0.46 0.05 0.99 1.50 0.16 3.01 6th 20th Il 0.04 0.62 0.08 0.13 2.01 0.26 20th Il 0.44 1.00 1.54 3.13

ro

Ul

σι
oo

tr · O

H W

2
H- X

ro

Ch cn ro
η η3

cn
cn>

3 > t

I *

ro η

O 2!

ro
η η

cn W

ricn

η w tr ¹ tr ¹ cn D

' The samples were placed in a climate of 20 ° C / 65 % r. F. removed and at

20 ° C / 95 % r. F. stored.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

K 2568 + H

Hi
1-( " Ll.
S- LO CD 8th CM CM ro t— * S- ΙΛ O CM ro 00 οι C3 O CTl CD O) (0 • S. CJ O IMe 0
C3 -LJ
(0 Ι CM ι- ΟΙ Ll. OO C. -σ ■ ^^ CD CM 00 O Oil S_ O CD CD σι ro :O LO CD CD , -T CM CM ta S- IO ε ej CJ | ü Oil O • σ CD CU CM B. S- • r- : <o _# ΙΛ Ll. ^} · I. Oil S- ro ro O CD 00 3: Q. δ ^ CD CD CD CM CM CM Oil (Λ LO CD CD ^ _ , _ , _ C3 Oil ro CJ ., _ co O CD ^ » CM (- \ _# O CD cn O Ll.
• O CD co 00 σι c§ «I. CD CD CD CD CD O O O : m CM OO "~ 00 CM * ~ »
^ * CD CD ^ ■ ^ » CD CD fs . * * - ' CD CU LO LO O S- O- LO LO LO LO rti UJ O LO

909808/0273

M.
LTI

Table IV

(D O <D 0 »O 00 * ·» O N> "4 to"

example Strength of size the Measurement duration Increase or decrease 20th (Wt .- *) the WDA _01n *) V6 Sample (mm) sample (mm ² ) (H) 20 ° C / 20% r.h. ' ° C / 35% r.h. 5.5 50> 100 4th -0.06 -0.03 8th -0.06 -0.03 8th 24 -0.06 -0.03 5.5 50 · 100 4th -0.48 -0.13 8th -0.51 -0.36 9 24 -0.53 -0.36 5.5 50 · 100 4th -1.31 -0.96 8th -1.36 -1.00 10 24 -1.40 -1.03 5.5 50- 100 4th -1.98 -1.47 8th -1.99 -1.52 24 -2.12 -1.57 20 ° C / 95% r.h. +0.39 +0.46 +0.80 +3.30 +3.81 +6.35 •
+6.51 +7.96 +13.51 +7.84 +12.17 +18.21

ro
cn

OO

f O
HW

ro
Dj cn

ro μ h (

H X
O Z ro
η ο

in tr) rt
cn

cn η

'All values are based on the initial WDA _QIN in a climate of 20 ° C / 65 % r. F. related.

Claims (1)

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG August 4, 1977 K 2568 + H -A ^ - WLK-Dr. I. -db Claims 1. Water vapor absorbent and permeable sheet-like structure made of natural or synthetic rubber or a rubber-like polymer with a uniformly incorporated additive of polymer particles, characterized in that it contains particles of at least one swellable, modified polymer as additive.
IO 2. Flat structure according to claim 1, characterized in that that the swellable, modified polymer is at least about 50% by weight water-insoluble. 3. Flat structure according to claim 1 or 2, characterized in that it is used as an additive of at least particles a swellable, modified carbohydrate derivative contains. 4. Flat structure according to one of claims 1 to 3, characterized in that it is used as an additive particles of at least one swellable, modified starch or Contains cellulose ether. 5. Flat structure according to one of claims 1 to 4, characterized in that the starch or cellulose ether by a with the help of thermal energy, radiation or by an additional chemical connection caused crosslinking was modified. . 909808/0273 HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG K 2568 + H - 2 - 6. Flat structure according to one of claims 1 to 5, characterized in that it is about 5 to 30 wt .-% Additive, based on the rubber content. 7. Process for the production of a water vapor absorbent and permeable sheet-like structure according to claim 1, characterized in that a rubber-containing Base mass, the particles of at least one swellable, modified polymer added and uniformly therein are distributed, and then the mixture, if necessary is foamed, spread or otherwise deformed and solidified. 8. The method according to claim 7, characterized in that that the particles in a proportion of 5 to 30 wt .-%, based on the rubber content of the finished sheet, can be added. 909808/0273